This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2001-401228, filed December 28, 2001, the entire contents of which are incorporated herein by reference.
1. Field of the Invention
The present invention relates to a novel color coupler compound, and relates to a silver halide color photosensitive material containing the novel color coupler compound and an image-forming method using the silver halide color photosensitive material. More particularly, the present invention relates to a silver halide color reversal photosensitive material and an image-forming method using the same.
2. Description of the Related Art
In recent years, the demands on silver halide color photosensitive materials for not only photographic speed increase, excellent sharpness and graininess but also faithful color reproduction to originals are strong.
In recent years, pyrazolotriazole couplers of low secondary absorption are in practical use as a magenta dye forming coupler. It has become apparent that pyrazolotriazole magenta couplers, although being compounds having excellent characteristics in hue, pose various problems such as low color-forming property, low resistance to processing variation and poor color image storability.
For example, couplers wherein the position for coupling with an oxidized aromatic primary amine developer is a hydrogen atom, known as 4-equivalent couplers, have drawbacks such as low color-forming property and yellow coloring upon aging after development processing, although the couplers are excellent in graininess. On the other hand, couplers having a coupling position substituted with a split-off group other than a hydrogen atom (for example, a halogen atom), known as 2-equivalent couplers, have a drawback in that the graininess is lowered to thereby result in deterioration of image quality, although the couplers are characterized in that, as compared with those of the 4-equivalent couplers, a color formation occurs with a decreased amount of silver and the possibility of yellow coloring is lowered.
Further, most of these couplers are used in the form of a solution or dispersion in a high-boiling organic solvent such as a phosphoric ester or a phthalic ester. In recent years, in accordance with the requirement for high sharpness, the amount of high-boiling organic solvent added tends to be reduced, and so-called oilless is demanded. However, with respect to most of pyrazolotriazole magenta couplers, extreme lowering of color-forming property is caused when they are used in an oilless state. Therefore, an improvement thereto is being demanded.
For solving the above problems, there have been proposed couplers based on pyrazolotriazoles wherein various ingenuities have been exerted onto substituents on the pyrazolotriazole ring. For example, with respect to the durability of color image, an improvement by a coupler having a 6-position substituent rendered bulky has been disclosed in U.S. Pat. No. 4,882,266 and E.P. 183,445.
Further, with respect to an improvement to color-forming property in an oilless state, a coupler having a carboxyl group introduced as a split-off group in the molecule thereof has been disclosed in Jpn. Pat. Appln. KOKAI Publication No. (hereinafter referred to as JP-A-) 1-102557.
However, these disclosed technologies have been unsatisfactory for the resolution of problems, such as yellow coloring by aging after processing and color image storability. Introduction of a split-off group, although an improvement in color-forming property can be recognized, causes couplers to suffer a cost increase and a poor crystallinity, thereby posing a problem in the industrial application. Moreover, additional problems, such as yellow staining of undyed portions by light irradiation or in humid heating atmosphere and occurrence of photographic speed drop during the stay from mixing with a color-sensitized silver halide emulsion through coating, have revealed. Still further, the resistance to variations of processing solution compositions is unsatisfactory, so that an improvement thereto has been demanded.
Most of the pyrazoloazole couplers now in practical use are 2-equivalent couplers. In the processing of color reversal photosensitive material, the first development is followed by reversal, and thereafter a color development processing is carried out. At this stage, the 2-equivalent couplers pose such an inherent problem that the color-forming property per mol of silver is high, thereby causing the photographic speed to be low as compared with those of the 4-equivalent couplers. Accordingly, when it is intended to apply a pyrazolotriazole magenta coupler to a color reversal photosensitive material, 4-equivalent couplers are preferably employed from the viewpoint of photographic speed. The application of 4-equivalent pyrazolotriazole magenta couplers to color reversal photosensitive materials is disclosed in, for example, JP-A""s 1-102557, 5-100382 (pages 13-15, 24-34, 42-45 and 53-63), 2001-33921 (pages 12-44) and 2001-324784 (pages 22-41). However, these disclosed technologies are not yet satisfactory for resolving the problems of durability to variations in processing solution compositions, and a solution to the problem of yellow coloring by aging after processing is desired.
It is the first object of the present invention to provide a magenta coupler capable of accomplishing stable image formation despite variations of processing solution compositions and further to provide a magenta coupler which realizes excellent color-forming property even in the reduction of high-boiling organic solvents, in so-called an oilless state. It is the second object of the present invention to provide a silver halide color photosensitive material which enables stable image formation despite variations of processing solution compositions, which exhibits excellent color reproducibility and durability, and which arises less stain.
The inventors have made extensive and intensive studies with a view toward obtaining a coupler which exhibits satisfactory color-forming property even in an oilless state, and also which arises less stain, which enables stable image formation despite variations of processing solution compositions, and which is excellent in graininess, image storability, etc. As a result, the present invention has been completed.
The objects of the present invention have been attained by the following means.
(1) A silver halide color photosensitive material comprising a 1H-pyrazolo[3,2-c]-1,2,4-triazole type coupler having, in its molecule, at least one substituent represented by the following general formula (I): 
wherein R1 represents a substituent, m represents an integer of 0 to 4, and R2 represents an alkyl group, alkenyl group or aryl group.
(2) The silver halide color photosensitive material according to item (1) above wherein the coupler described in item (1) above is represented by the following general formula (II): 
wherein R3 represents a substituent; X1 represents a hydrogen atom or a group capable of splitting-off upon reaction with an oxidized developing agent; R4 and R5 each independently represents a hydrogen atom, alkyl group, or aryl group; and n represents an integer of 1 to 3. M represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)N(R6)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94SO2N(R6)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94C(R6)C(xe2x95x90O)N(R7)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R6)xe2x80x94, wherein R6 and R7 each independently represents a hydrogen atom, alkyl group or aryl group; L1 represents an alkylene group, aralkylene group or arylene group; and p represents 0 or 1. * represents the position at which the group represented by the general formula (I) is attached.
(3). A silver halide color photosensitive material comprising at least one coupler represented by the following general formula (III) or general formula (IV): 
wherein R8 represents a substituent; X2 represents a hydrogen atom or a group capable of splitting-off upon reaction with an oxidized developing agent. L2 represents an alkylene group or aralkylene group; Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)N(R10)xe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, xe2x80x94C(xe2x95x90O)N(R9)xe2x80x94 or xe2x80x94C(xe2x95x90O)Oxe2x80x94, wherein R9 and R10 each independently represents a hydrogen atom, alkyl group or aryl group. Y1 represents a divalent linking group, and q represents 0 or 1. R11 and R12 each independently represents a hydrogen atom, alkyl group or aryl group, and A1 represents a group represented by the following general formula (V) or a group having a group represented by the following general formula (V): 
Wherein R13 and R14 each independently represents a substituent, s represents in integer of 0 to 5; and t represents an integer of 0 to 3. R15 represents an alkyl group or aryl group; and Z2 represents xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94C(xe2x95x90O)N(R16)xe2x80x94, xe2x80x94SO2xe2x80x94 or xe2x80x94SO2N(R16)xe2x80x94, wherein R16 represents a hydrogen atom, alkyl group or aryl group.
(4) The silver halide color photosensitive material according to item (3) above, wherein L2 in the general formula (III) is represented by the following general formula (VI): 
wherein R17, R18, R19 and R20 each independently represents a hydrogen atom, alkyl group or aryl group; and a represents an integer of 0 to 2. ** represents a position at which L2 attaches to the pyrazolotriazole skeleton of the coupler represented by the general formula (III); and *** represents a position to which Z1 in the general formula (III) attaches.
(5) The silver halide color photosensitive material according to item (3) or (4) above, wherein the group represented by A1 in the general formula (III) and general formula (IV) is represented by the following general formula (VII): 
wherein R13 and R14 each independently represents a substituent, s represents an integer of 0 to 5; and t represents an integer of 0 to 3. R15 represents an alkyl group or aryl group; and Z2 represents xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94C(xe2x95x90O)N(R16)xe2x80x94, xe2x80x94SO2xe2x80x94 or xe2x80x94SO2N(R16)xe2x80x94, wherein R16 represents a hydrogen atom, alkyl group or aryl group.
(6) The silver halide color photosensitive material according to any one of items (1) to (5), wherein the coupler described in the items (1) to (5) is a coupler represented by the following formula (VIII): 
wherein R1 represents a substituent; m represents an integer of 0 to 4; and R2 represents an alkyl group, alkenyl group or aryl group. R3 represents a substituent, and X1 represents a hydrogen atom or a group capable of splitting-off upon reaction with an oxidized developing agent. R4 and R5 each independently represents a hydrogen atom, alkyl group, or aryl group; and n represents an integer of 1 to 3. M represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)N(R6)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94SO2N(R6)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94C(R6)C(xe2x95x90O)N(R7)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R6)xe2x80x94, wherein R6 and R7 each independently represents a hydrogen atom, alkyl group or aryl group. R13 and R14 each independently represents a substituent, s represents an integer of 0 to 5; and t represents an integer of 0 to 3.
(7) The silver halide color photosensitive material according to any one of items (2) to (6) above, wherein R3 in the general formula (II) and general formula (VIII), and R8 in the general formula (III) and general formula (IV) each represents a tertiary alkyl group.
(8) The silver halide color photosensitive material according to any one of items (2) to (7) above, wherein X1 in the general formula (II) and general formula (VIII), and X2 in the general formula (III) and general formula (IV) each represents a hydrogen atom.
(9) The silver halide color photosensitive material according to any one items (1) to (8) above further comprising the following compound SR-1: 
Additional objects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out hereinafter.
The present invention will be described in detail below.
R1, m and R2 of the general formula (I) will be described in detail.
R1 in the general formula (I) represents a substituent. The substituent represented by R1 includes halogen atom (e.g., a fluorine atom, a chlorine atom or a bromine atom); an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms (hereinafter the groups containing an alkyl moiety such as a alkoxy group and so on have the same meaning), such as methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-norbornyl or 1-adamantyl); an alkenyl group (preferably an alkenyl group having 2 to 48 carbon atoms, such as vinyl, allyl or 3-buten-1-yl); an aryl group (preferably an aryl group having 6 to 48 carbon atoms, such as phenyl or naphthyl); a heterocyclic group (preferably a heterocyclic group having 1 to 32 carbon atoms and having at least one hetero atom selected from a group consisting of N, S, O and P, and an aromatic ring such as a benzene ring may be fused thereto (hereinafter groups containing a heterocyclic moiety such as a heterocyclic oxy group and so on have the same meaning), such as 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1-pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl or benzotriazol-1-yl); a silyl group (preferably a silyl group having 3 to 38 carbon atoms, such as trimethylsilyl, triethylsilyl, tributylsilyl, t-butyldimethylsilyl or t-hexyldimethylsilyl); a hydroxyl group; a cyano group; a nitro group; an alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, such as methoxy, ethoxy, 1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy or a cycloalkyloxy group (e.g., cyclopentyloxy or cyclohexyloxy)); an aryloxy group (preferably an aryloxy group having 6 to 48 carbon atoms, such as phenoxy or 1-naphthoxy); a heterocyclic oxy group (preferably a heterocyclic oxy group having 1 to 32 carbon atoms, such as 1-phenyltetrazol-5-oxy or 2-tetrahydropyranyloxy); a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy or diphenylmethylsilyloxy); an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, such as acetoxy, pivaloyloxy, benzoyloxy or dodecanoyloxy); an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, such as ethoxycarbonyloxy, t-butoxycarbonyloxy or a cycloalkyloxycarbonyloxy group (e.g., cyclohexyloxycarbonyloxy)); an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, such as phenoxycarbonyloxy); a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, such as N,N-dimethylcarbamoyloxy, N-butylcarbamoyloxy, N-phenylcarbamoyloxy or N-ethyl-N-phenylcarbamoyloxy); a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, such as N,N-diethylsulfamoyloxy or N-propylsulfamoyloxy); an alkylsulfonyloxy group (preferably an alkylsulfonyloxy group having 1 to 38 carbon atoms, such as methylsulfonyloxy, hexadecylsulfonyloxy or cyclohexylsulfonyloxy); an arylsulfonyloxy group (preferably an arylsulfonyloxy group having 6 to 32 carbon atoms, such as phenylsulfonyloxy); an acyl group (preferably an acyl group having 1 to 48 carbon atoms, such as formyl, acetyl, pivaloyl, benzoyl, tetradecanoyl or cyclohexanoyl); an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl or cyclohexyloxycarbonyl); an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, such as phenoxycarbonyl); a carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, such as carbamoyl, N,N-diethylcarbamoyl, N-ethyl-N-octylcarbamoyl, N,N-dibutylcarbamoyl, N-propylcarbamoyl, N-phenylcarbamoyl, N-methyl-N-phenylcarbamoyl or N,N-dicyclohexylcarbamoyl); an amino group (preferably an amino group having 32 or less carbon atoms, such as amino, methylamino, N,N-dibutylamino, tetradecylamino, 2-ethylhexylamino or cyclohexylamino); an anilino group (preferably an anilino group having 6 to 32 carbon atoms, such as anilino or N-methylanilino); a heterocyclic amino group (preferably a heterocyclic amino group having 1 to 32 carbon atoms, such as 4-pyridylamino); a carbonamido group (preferably a carbonamido group having 2 to 48 carbon atoms, such as acetamido, benzamido, tetradecanamido, pivaloylamido or cyclohexanamido); a ureido group (preferably a ureido group having 1 to 32 carbon atoms, such as ureido, N,N-dimethylureido or N-phenylureido); an imido group (preferably an imido group having 10 or less carbon atoms, such as N-succinimido or N-phthalimido); an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 48 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino or cyclohexyloxycarbonylamino); an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, such as phenoxycarbonylamino); a sulfonamido group (preferably a sulfonamido group having 1 to 48 carbon atoms, such as methanesulfonamido, butanesulfonamido, benzenesulfonamido, hexadecanesulfonamido or cyclohexanesulfonamido); a sulfamoylamino group (preferably a sulfamoylamino group having 1 to 48 carbon atoms, such as N,N-dipropylsulfamoylamino or N-ethyl-N-dodecylsulfamoylamino); an azo group (preferably an azo group having 1 to 32 carbon atoms, such as phenylazo or 3-pyrazolylazo); an alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, such as methylthio, ethylthio, octylthio or cyclohexylthio); an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, such as phenylthio); a heterocyclic thio group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, such as 2-benzothiazolylthio, 2-pyridylthio or 1-phenyltetrazolylthio); an alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, such as dodecanesulfinyl); an arylsulfinyl group (preferably an arylsulfinyl group having 6 to 32 carbon atoms, such as phenylsulfinyl); an alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, isopropylsulfonyl, 2-ethylhexylsulfonyl, hexadecylsulfonyl, octylsulfonyl or cyclohexylsulfonyl); an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, such as phenylsulfonyl or 1-naphthylsulfonyl); a sulfamoyl group (preferably a sulfamoyl group having 32 or less carbon atoms, such as sulfamoyl, N,N-dipropylsulfamoyl, N-ethyl-N-dodecylsulfamoyl, N-ethyl-N-phenylsulfamoyl or N-cyclohexylsulfamoyl); a sulfo group; a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, such as phenoxyphosphonyl, octyloxyphosphonyl or phenylphosphonyl); or a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, such as diethoxyphosphinoylamino or dioctyloxyphosphinoylamino).
When R1 represents a group capable of further being substituted, it may be substituted with any of the above substituents. When it is substituted with two or more substituents, these substituents may be the same or different. When it is substituted with two or more substituents, these may be bonded together thereby forming a ring (hereinafter the same can be applied to the case where a substituent is further substituted with two or more substituent).
m represents an integer of 0 to 4. When m represents 2 or more, a plurality of R1""s may be the same or different.
In the general formula (I), R2 represents an alkyl group, alkenyl group or aryl group. Preferable ranges of the alkyl group, alkenyl group and aryl group are the same as the alkyl group, alkenyl group and aryl group described above as R1, respectively. The alkyl group, alkenyl group or aryl group represented by R2 may be substituted by a substituent described above as R1. When the alkyl group, alkenyl group or aryl group represented by R2 is substituted by two or more substituents, those substituents may be the same or different.
Representative specific examples of the general formula (I) are set forth below, but the present invention is not limited to these.
The group represented by the general formula (I) may be attached to a substituent at 3-, 6- or 7-position of 1H-pyrazolo[3,2-c]-1,2,4-triazole type coupler. The number of the group represented by the general formula (I) may be two or more. When the coupler has two or more groups represented by the general formula (I), the groups may have the same structure or may be different.
The 1H-pyrazolo[3,2-c]-1,2,4-triazole type coupler having the group represented by the general formula (I) is preferably represented by the above general formula (II).
Next, the general formula (II) will be described in detail.
In the formula (II), R3 represents a substituent. Preferable range of the substituent represented by R3 is the same as the substituent represented by R1 described above. When the substituent represented by R3 represents a group capable of having a further substituent, R3 may have a substituent described above as R1. When R3 has two or more substituents, those substituents may be the same or different.
In the general formula (II), R4 and R5 each independently represents a hydrogen atom, alkyl group or aryl group. The alkyl group and aryl group represented by R4 and R5 have the same meaning as the alkyl group and aryl group described above as R1, respectively. The alkyl group and aryl group represented by R4 and R5 may have a substituent described above as R1. When the alkyl group and the aryl group have two or more substituents, those substituents may be the same or different.
n represents an integer of 1 to 3.
In the general formula (II), M represents xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SOxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94C(xe2x95x90O)N(R6)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94SO2N(R6)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94C(R6)C(xe2x95x90O)N(R7)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R6)xe2x80x94, wherein in each of the formulas, the left hand side bonding attaches to xe2x80x94{C(R4)(R5)}nxe2x80x94 of the general formula (II). R6 and R7 each independently represents a hydrogen atom, alkyl group or aryl group.
The alkyl group and aryl group represented by R6 and R7 have the same meaning as the alkyl group and aryl group described above as R1, respectively. The alkyl group and aryl group represented by R6 and R7 may have a substituent described above as R1. When the alkyl group and the aryl group have two or more substituents, those substituents may be the same or different.
L1 of the general formula (II) represents an alkylene group, arylene group or aralkylene group. In particular, L1 represents an alkylene group (alkylene group having 1 to 48 carbon atoms, preferably 1 to 18 carbon atoms, such as methylene, ethylene, propylene or butylene), aralkylene group (aralkylene group having 7 to 48 carbon atoms, preferably 7 to 18 carbon atoms, wherein the aralkylene group includes both groups of -alkylene-arylene- and -arylene-alkylene-, such as divalent benzyl or divalent phenethyl), or arylene group (arylene group having 6 to 48, preferable 6 to 18 carbon atom, such as o-phenylene, m-phenylene, p-phenylene, or 1,4-naphthalene). When the alkylene group, aralkylene group and arylene group are capable of being substituted, the alkylene, aralkylene and arylene groups may be substituted with a substituent described above as R1. When the alkylene, aralkylene and arylene groups are substituted with two or more substituents, these substituents may be the same or different.
p represents 0 or 1, and * represents the position at which the group represented by the general formula (I) is attached.
X1 of the general formula (II) represents a hydrogen atom, or a group capable of splitting-off upon reaction with an oxidized developing agent. Specific examples of X1 includes a hydrogen atom, halogen atom, alkoxy group, aryloxy group, heterocyclicoxy group, acyloxy group, alkoxycarbonyloxy group, carbamoyloxy group, alkylthio group, arylthio group, heterocyclic thio group, imido group azo group or aromatic heterocyclic group with its nitrogen atom attached to the coupling active position. Preferable ranges of these hydrogen atom, halogen atom, alkoxy group, aryloxy group, heterocyclicoxy group, acyloxy group, alkoxycarbonyloxy group, carbamoyloxy group, alkylthio group, arylthio group, heterocyclic thio group, imido group azo group and aromatic heterocyclic group with its nitrogen atom attached to the coupling active position, the same as those described above as R1, respectively. When each of these groups represented by X1 is a group capable of being further substituted, these groups represented by X1 may be substituted by a substituent described above as R1. When each of these groups represented by X1 is substituted by two or more substituents, those substituents may be the same or different.
Next, preferable range of the coupler of the invention having the group represented by the general formula (I) will be described.
A preferable coupler is one having the group represented by the general formula (I) that is attached at the position marked with * in the 1H-pyrazolo[3,2-c]-1,2,4-triazole type coupler represented by the general formula (II).
More preferable coupler is, in the general formula (II), R3 represents an alkyl group, aryl group, alkoxy group, aryloxy group, anilino group, carbonamido group or alkoxycarbonylamino group, X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 1 to 3, p represents 0 or 1, wherein when p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, wherein R6 and R7 represents a hydrogen atom, L1 represents an alkylene group or arylene group, and in the general formula (I), R1 represents a halogen atom, alkyl group, aryl group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, alkoxycarbonyl group, carbamoyl group carbonamido group ureido group, alkoxycarbonylamino group, sulfonamido group, alkylthio group, arylthio group, alkylsulfonyl group arylsulfonyl group or sulfamoyl group, m represents 0 or 1, and R2 represents an alkyl group or aryl group.
More preferable coupler is, in the general formula (II), R3 represents an alkyl group, X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 1 to 3, p represents 0 or 1, wherein when p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, R6 and R7 represents a hydrogen atom, L1 represents an alkylene group or arylene group, and in the general formula (I), R1 represents a halogen atom or alkyl group, m represents 0 or 1, and R2 represents an alkyl group or aryl group.
Much more preferable coupler is, in the general formula (II), R3 represents a tertiary alkyl group, X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 1 to 3, p represents 0 or 1, wherein when p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, each of R6 and R7 represents a hydrogen atom, L1 represents an alkylene group or arylene group, and in the general formula (I), R1 represents a halogen atom or alkyl group, m represents 0 or 1, and R2 represents an alkyl group or aryl group.
Still much more preferable coupler is, in the general formula (II), R3 represents a tertiary alkyl group, X1 represents a hydrogen atom or halogen atom, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 1 to 3, p represents 0 or 1, wherein when p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, wherein each of R6 and R7 represents a hydrogen atom, L1 represents an alkylene group or arylene group, and in the general formula (I), R1 represents a halogen atom or alkyl group, m represents 0 or 1, and R2 represents an alkyl group or aryl group.
Still much more preferable coupler is, in the general formula (II), R3 represents a tertiary alkyl group, X1 represents a hydrogen atom or halogen atom, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 1 to 2, p represents 0 or 1, wherein when p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94 or xe2x80x94N(R6)SO2xe2x80x94, wherein R6 represents a hydrogen atom, L1 represents an alkylene group or arylene group, and in the general formula (I), R1 represents a halogen atom or alkyl group, m represents 0 or 1, and R2 represents an alkyl group or aryl group.
Still much more preferable coupler is, in the general formula (II), R3 represents a tertiary alkyl group, X1 represents a hydrogen atom, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 1 to 2, p represents 0 or 1, wherein when p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94 or xe2x80x94N(R6)SO2xe2x80x94, wherein R6 represents a hydrogen atom, L1 represents an alkylene group or arylene group, and in the general formula (I), m represents 0, and R2 represents an alkyl group or aryl group.
Most preferable coupler is, in the general formula (II), R3 represents a tertiary alkyl group, X1 represents a hydrogen atom, R4 represents a hydrogen atom or methyl group, R5 represents a methyl group, n represents an integer of 1 to 2, p represents 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94 or xe2x80x94N(R6)SO2xe2x80x94, wherein R6 represents a hydrogen atom, L1 represents an alkylene group, and in the general formula (I), m represents 0, and R2 represents an alkyl group or aryl group.
Next, representative specific examples of the coupler of the present invention having a substituent represented by the general formula (I) are shown, but the present invention is not limited to these.
Next, the coupler represented by the general formula (III) and general formula (IV) will be described in detail.
R8 in the general formula (III) and general formula (IV) represents a substituent, which has the same meaning as the group described above as R3. When the substituent represented by R8 represents a group capable of having a further substituent, R8 may be substituted with a substituent described above as R1. When R8 is substituted with two or more substituents, those substituents may be the same or different.
X2 in the general formula (III) and general formula (IV) represents a hydrogen atom or a group capable of splitting-off group upon reaction with an oxidized developing agent, which has the same meaning as the above X1. X2 may be substituted with a substituent described above as R1. When X2 is substituted with two or more substituents those substituents may be the same or different.
L2 in the general formula (III) represents an alkylene group or aralkylene group. The alkylene group, aralkylene group and arylene group have the same meaning as the alkylene group, aralkylene group or arylene group, respectively, described above as L1. When the alkylene group and aralkylene group represented by L2 are groups capable of being further substituted, L2 may be substituted with a substituent described above as R1. When L2 is substituted with two or more substituents, those substituents may be the same or different.
Y1 in the general formula (III) and general formula (IV) represents a divalent linking group, for example, an alkylene group, aralkylene group, arylene group, xe2x80x94Oxe2x80x94, xe2x80x94Sxe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94N(R21)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R21)C(xe2x95x90O)Oxe2x80x94, xe2x80x94N(R21)C(xe2x95x90O)N(R22)xe2x80x94, xe2x80x94N(R21)SO2xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94, xe2x80x94C(xe2x95x90O)N(R21)xe2x80x94 or xe2x80x94SO2N(R22)xe2x80x94, wherein each of the linking groups bonds, through its left hand bonding, toward the direction of Z1 of the general formula (III) or toward the direction of xe2x80x94NHSO2xe2x80x94 of the general formula (IV). Further, a plurality of the above divalent groups may be bonded to each other thereby forming a new divalent linking group. When two or more groups are bonded thereby forming a new divalent linking group, those groups may be the same or different. When the divalent group represented by Y1 represents a group capable of being further substituted, Y1 may be substituted with a substituent described above as R1. When Y1 represents substituted with two or more substituents, those substituents may be the same or different.
R21 and R22 each independently represents a hydrogen atom, alkyl group or aryl group. Preferable ranges of the alkyl group and aryl group represented by R21 and R22 are the same as the alkyl group and aryl group which are described above as R1, respectively. The alkyl group and aryl group represented by R21 and R22 may be substituted by a substituent described above as R1. When the alkyl group and aryl group represented by R21 and R22 are substituted by two or more substituents, those substituents may be the same or different.
q represents 0 or 1.
Z1 in the general formula (III) represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)N(R10)xe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, xe2x80x94C(xe2x95x90O)N(R9)xe2x80x94 or xe2x80x94C(xe2x95x90O)Oxe2x80x94, wherein each of the groups bonds to L2 of the general formula (III) through its left hand bonding. R9 and R10 independently represents a hydrogen atom, alkyl group or aryl group. Preferable ranges of the alkyl group and aryl group represented by R9 and R10 are the same as the alkyl group and aryl group which are described above as R1, respectively. The alkyl group and aryl group represented by R9 and R10 may be substituted by a substituent described above as R1. When the alkyl group and aryl group represented by R9 and R10 are substituted by two or more substituents, those substituents may be the same or different.
R11 and R12 in the general formula (IV) each independently represents a hydrogen atom, alkyl group or aryl group. Preferable ranges of the alkyl group and aryl group are the same as the alkyl group and aryl group described above as R1, respectively.
A1 in the general formula (III) and general formula (IV) is represented by the general formula (V).
R13, R14, R15, Z2, s and t of the general formula (V) will be described.
R13 and R14 in the general formula (V) each independently represents a substituent. The substituent represented by R13 and R14 has the same meaning as the substituent described above as R1. When the substituent represented by R13 and R14 represents a group capable of having a further substituent, R13 and R14 may have a substituent described above as R1. When R13 and R14 have two or more substituents, those substituents may be the same or different.
s represents an integer of 0 to 5. t represents an integer of 0 to 3. t preferably represents 0.
R15 in the general formula (V) represents an alkyl group or aryl group. Preferable ranges of the alkyl group and aryl group represented by R15 are the same as the alkyl group and aryl group which are described above as R1, respectively. The alkyl group and aryl group represented by R15 may be substituted by a substituent described above as R1. When the alkyl group and aryl group represented by R15 are substituted by two or more substituents, those substituents may be the same or different.
Z2 in the general formula (V) represents xe2x80x94C(xe2x95x90O)xe2x80x94, xe2x80x94SO2xe2x80x94, xe2x80x94C(xe2x95x90O)N(R16)xe2x80x94, xe2x80x94C(xe2x95x90O)Oxe2x80x94 or xe2x80x94SO2N(R16)xe2x80x94, wherein each of the groups bonds to xe2x80x94NHxe2x80x94 of the general formula (V) through its left hand bonding. R16 represents a hydrogen atom, alkyl group or aryl group. Preferable ranges of the alkyl group and aryl group represented by R16 are the same as the alkyl group and aryl group described above as R1, respectively. The alkyl group and aryl group represented by R16 may be substituted by a substituent that is described above as R1. When the alkyl group and aryl group represented by R16 are substituted by two or more substituents, those substituents may be the same or different.
The substitution positions of the three substituents, xe2x80x94NHxe2x80x94(Z2)xe2x80x94R15, xe2x80x94(R14)t, and xe2x80x94O-phenylene-(R13)s, are not particularly limited, but xe2x80x94O-phenylene-(R13)s preferably substitute at ortho-position, and xe2x80x94NHxe2x80x94(Z2)xe2x80x94R15 preferably substitute at meta-position. In the group of xe2x80x94O-phenylene xe2x80x94(R13)s, xe2x80x94R13 may be substituted at any position from a viewpoint of the performance of the coupler. From a viewpoint of availability of a raw material for the coupler, xe2x80x94R13 preferably substitutes at ortho- and/or para-position, and more preferably substitutes at para-position.
L2 in the general formula (III) is preferably represented by the general formula (VI).
R17, R18, R19 and R20 in the general formula (VI) each independently represents a hydrogen atom, alkyl group or aryl group. Preferable ranges of the alkyl group and aryl group are the same as the alkyl group and aryl group described above as R1, respectively. The alkyl group and aryl group represented by R17, R18, R19 and R20 may be substituted with a substituent described above as R1. When R17, R18, R19 and R20 have two or more substituents, those substituents may be the same or different.
a in the general formula (VI) represents an integer of 0 to 2.
** represents the position at which it attaches to the pyrazolotriazole skeleton of the general formula (III). *** represents the position to which Z1 in the general formula (III) attaches.
A1 in the general formula (III) and the general formula (IV) preferably represents the group represented by the general formula (VII).
R13, R14, R15, R16, Z2, s and t of the general formula (VII) have the same meaning as those in the general formula (V), respectively.
Next, the general formula (VIII) will be described.
R1, m and R2 of the general formula (VIII) have the same meaning as those described above for the general formula (I), respectively.
R3, R4, R5, X1 and M of the general formula (VIII) have the same meaning as those described above for the general formula (II), respectively.
R13, R14, s and t of the general formula (V) have the same meaning as those described above for the general formula (V), respectively.
Next, preferable range of the coupler represented by the general formula (III) and general formula (IV) will be described.
Preferable coupler is, in the general formula (III) and general formula (IV), R8 represents an alkyl group, aryl group, alkoxy group, aryloxy group, anilino group, carbonamido group, alkoxycarbonylamino group or sulfonamido group, X2 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring, L2 represents an alkylene group, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, Y1 represents an alkylene group, aralkylene group or arylene group, q represents 0 or 1, and A1 is represented by the general formula (V).
More preferable coupler is, in the general formula (III) and general formula (IV), R8 represents an alkyl group, aryl group, alkoxy group or aryloxy group, X2 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring, L2 represents an alkylene group, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, Y1 represents an alkylene group, aralkylene group or arylene group, q represents 0 or 1, and A1 is represented by the general formula (V).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents an alkyl group, aryl group, alkoxy group or aryloxy group, X2 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring, L2 is represented by the general formula (VI), Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, Y1 represents an alkylene group, aralkylene group or arylene group, q represents 0 or 1, and A1 is represented by the general formula (V).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents an alkyl group, X2 represents a hydrogen atom or halogen atom, L2 is represented by the general formula (VI), Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, Y1 represents an alkylene group, aralkylene group or arylene group, q represents 0 or 1, and A1 is represented by the general formula (V).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom or halogen atom, L2 is represented by the general formula (VI), Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, Y1 represents an alkylene group, aralkylene group or arylene group, q represents 0 or 1, and A1 is represented by the general formula (V).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom or halogen atom, L2 is represented by the general formula (VI), Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94, xe2x80x94OC(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)N(R9)xe2x80x94, wherein R9 represents a hydrogen atom, Y1 represents an alkylene group, aralkylene group or arylene group, q represents 0 or 1, and A1 is represented by the general formula (VII).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom, L2 is represented by the general formula (VI), wherein each of R17, R18, R19, and R20 independently represents a hydrogen atom or methyl group, and a represents 0, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R9)C(xe2x95x90O)Oxe2x80x94 or xe2x80x94OC(xe2x95x90O)xe2x80x94, wherein R9 represents a hydrogen atom, q represents 0, and A1 is represented by the general formula (VII).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom, L2 is represented by the general formula (VI), wherein each of R17, R18, R19, and R20 independently represents a hydrogen atom or methyl group, and a represents 0, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)xe2x80x94, wherein R9 represents a hydrogen atom, q represents 0, and A1 is represented by the general formula (VII).
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom, L2 is represented by the general formula (VI), wherein each of R17, R18, R19, and R20 independently represents a hydrogen atom or methyl group, and a represents 0, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)xe2x80x94, wherein R9 represents a hydrogen atom, q represents 0, and A1 is represented by the general formula (VII), wherein R13 represents an alkyl group, halogen atom, aryl group, alkoxy group, aryloxy group, carbonamido group, sulfonamido group, alkoxycarbonyl group, sulfonyl group, cyano group or imido group, s represents an integer of 0 to 2, t represents 0, Z2 represents xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94SO2xe2x80x94, and R15 represents an alkyl group or aryl group.
Still more preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom, L2 is represented by the general formula (VI), wherein each of R17, R18, R19, and R20 independently represents a hydrogen atom or methyl group, and a represents 0, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)xe2x80x94, wherein R9 represents a hydrogen atom, q represents 0, and A1 is represented by the general formula (VII), wherein R13 represents an alkyl group, halogen atom, alkoxy group, carbonamido group, sulfonamido group, alkoxycarbonyl group or sulfonyl group, s represents an integer of 0 to 2, t represents 0, Z2 represents xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94SO2xe2x80x94, and R15 represents an alkyl group or aryl group.
Most preferable coupler is, in the general formula (III) and general formula (IV), R8 represents a tertiary alkyl group, X2 represents a hydrogen atom, L2 is represented by the general formula (VI), wherein each of R17, R18, R19, and R20 independently represents a hydrogen atom or methyl group, and a represents 0, Z1 represents xe2x80x94N(R9)C(xe2x95x90O)xe2x80x94 or xe2x80x94OC(xe2x95x90O)xe2x80x94, wherein R9 represents a hydrogen atom, q represents 0, and A1 is represented by the general formula (VII), wherein R13 represents an alkyl group, halogen atom, alkoxycarbonyl group or alkoxy group, s represents an integer of 0 to 2, t represents 0, Z2 represents xe2x80x94C(xe2x95x90O)xe2x80x94 or xe2x80x94SO2xe2x80x94, and R15 represents an alkyl group or aryl group.
Preferable range of the couplers represented by the general formula (VIII) will be described.
Preferable coupler is, in the general formula (VIII), R1 represents a halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, aminocarbonylamino group, sulfonamido group or imido group, m represents an integer of 0 to 2, R2 represents an alkyl group or aryl group, R3 represents an alkyl group, aryl group, alkoxy group, aryloxy group, acylamino group, anilino group, alkylthio group, arylthio group or carbamoyl group, R4 and R5 each independently represents a hydrogen atom, alkyl group or aryl group, n represents an :integer of 0 to 3, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, wherein R6 and R7 each independently represents a hydrogen atom or alkyl group, R13 represents a substituent, s represents an integer of 0 to 3, R14 represents a substituent, t represents in integer of 0 to 2, and X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, imido group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring.
Still more preferable coupler is, in the general formula (VIII), R1 represents a halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, aminocarbonylamino group or sulfonamido group, m represents an integer of 0 to 1, R2 represents an alkyl group or aryl group, R3 represents an alkyl group, aryl group, alkoxy group, aryloxy group or acylamino group, R4 and R5 each independently represents a hydrogen atom or alkyl group, n represents an integer of 0 to 2, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, wherein R6 and R7 each independently represents a hydrogen atom or alkyl group, R13 represents a substituent, R14 represents a substituent, t represents 0 or 1, and X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, imido group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring.
Still more preferable coupler is, in the general formula (VIII), R1 represents a halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, aminocarbonylamino group or sulfonamido group, m represents an integer of 0 to 1, R2 represents an alkyl group or aryl group, R3 represents an alkyl group, R4 and R5 each independently represents a hydrogen atom or methyl group, n represents an integer of 0 to 2, M represents. xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, wherein R6 and R7 each represents a hydrogen atom, R13 represents a substituent, s represents an integer of 0 to 3, R14 represents a substituent, t represents 0 or 1, and X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, imido group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring.
Still more preferable coupler is, in the general formula (VIII), R1 represents a halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, acylamino group, alkoxycarbonylamino group, aminocarbonylamino group or sulfonamido group, m represents an integer of 0 to 1, R2 represents an alkyl group or aryl group, R3 represents a tertiary alkyl group, R4 and R5 each independently represents a hydrogen atom or methyl group, n represents an integer of 0 to 2, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)SO2xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)N(R7)xe2x80x94 or xe2x80x94N(R6)C(xe2x95x90O)Oxe2x80x94, R6 arid R7 each represents a hydrogen atom, R13 represents a substituent, s represents an integer of 0 to 3, R14 represents a substituent, t represents 0 or 1, and X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, imido group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring.
Still more preferable coupler is, in the general formula (VIII), m represents 0, R2 represents an alkyl group or aryl group, R3 represents a tertiary alkyl group, R4 and R5 each independently represents a hydrogen atom or methyl group, n represents 0 or 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94 or xe2x80x94N(R6)SO2xe2x80x94, wherein R6 represents a hydrogen atom, R13 represents a substituent, s represents an integer of 0 to 3, t represents 0, and X1 represents a hydrogen atom, halogen atom, aryloxy group, alkylthio group, arylthio group, imido group or aromatic heterocyclic group with its nitrogen atom attached to the pyrazolotriazole ring.
Most preferable coupler is, in the general formula (VIII), m represents 0, R2 represents an alkyl group or aryl group, R3 represents a tertiary alkyl group, R4 and R5 each independently represents a hydrogen atom or methyl group, n represents 0 or 1, M represents xe2x80x94OC(xe2x95x90O)xe2x80x94, xe2x80x94N(R6)C(xe2x95x90O)xe2x80x94 or xe2x80x94N(R6)SO2xe2x80x94, R6 represents a hydrogen atom, R13 represents a substituent, s represents an integer of 0 to 3, t represents 0, and X1 represents a hydrogen atom.
Next, representative specific examples of the couplers represented by the general formula (III), general formula (IV) and general formula (VIII) are shown, but the present invention is not limited to these.
Next, a synthetic method of the coupler of the present invention will be described.
(Synthetic example 1)
Exemplified Coupler MA-7 was synthesized in accordance with the following reaction scheme A. 
(Synthesis of Intermediate A)
400 milliliter (hereinafter milliliter is also referred to as xe2x80x9cmLxe2x80x9d) of dimethylacetamide was added to 151.2 g (1.0 mol) of methyl anthranilate, and agitated at room temperature. To the solution, 190.65 (1.0 mol) of p-toluenesulfonyl chloride was added. After the completion of the addition, 89 mL (1.1 mol) of pyridine was dropped to the reaction solution. After the completion of the dropping, the solution was agitated at room temperature for 3 hr, to complete the reaction. The reaction solution was pored into 200 mL of water while agitating, to precipitate crystal. The reaction solution was filtered and the crystal was harvested, washed with water, dried to obtain 285.5 g (yield: 93.5%) of intermediate A.
(Synthesis of Intermediate B)
450 mL of methanol was added to 152.7 g (0.5 mol) of intermediate A obtained by the above procedure, and agitated at room temperature. To the solution, an aqueous solution obtained by dissolving 60.0 g (1.5 mol) of sodium hydroxide to 300 mL of water was added, and heated to 40xc2x0 C. This reaction mixture was agitated for 2 hr to complete the reaction. After that, the reaction solution was cooled to room temperature and then 2000 mL of water was added. To the solution, 170 mL of concentrated hydrochloric acid was added to acidify the solution, thereby to precipitate crystal. The solution was filtered to obtain the crystal, washed with water, dried, to obtain 134.0 g (yield: 92.3%) of intermediate B.
(Synthesis of Intermediate C)
260 mL of toluene was added to 87.4 g (0.3 mol) of intermediate B obtained by the above procedure, heated to 80xc2x0 C., and agitated. To this suspension, 28.5 mL of thionyl chloride was dropped. After the completion of the dropping, the intermediate B solution was heated to 80xc2x0 C., and agitated for 2 hr. After the completion of the reaction, excessive thionyl chloride and toluene, solvent, were distilled-off. After cooling, crystal of intermediate C was obtained in a quantitative manner, which was subjected to the subsequent step of the reaction.
(Synthesis of Intermediate D)
1900 mL of dimethylformamide was added to 243.3 g (0.9 mol) of stearoyl alcohol, and agitated at room temperature. 95.1 g (0.99 mol) of sodium t-butoxide was added to this solution and heated to 80xc2x0 C. to 90xc2x0 C. for 2 hr. After cooling the solution to 50xc2x0 C., 223.6 g (1.0 mol) of sodium 2-chloro-5-nitrobenzoate was added, and heated to 80xc2x0 C. to 90xc2x0 C., and agitated for 2 hr to complete the reaction. 2000 mL of acetonitrile was added to this reaction solution, and precipitated crystal. The reaction solution was cooled to 15xc2x0 C., and agitated for 1 hr. The reaction solution was filtered-off, harvested the crystal, washed with 400 mL of acetonitrile and further with water, and dried to obtain 352 g (yield: 85.5%) of intermediate D.
(Synthesis of Intermediate E)
400 mL of acetonitril and 1.0 mL of dimethylformamide were added to 100 g (0.24 mol) of intermediate D obtained by the above procedure, and heated to 75xc2x0 C. and agitated. 36.5 mL (0.5 mol) of thionyl chloride was dropped. After the completion of the dropping, the solution was heated and agitated for 2 hr to complete the reaction. After the completion of the reaction, excessive thionyl chloride and toluene, solvent, were distilled-off under reduced pressure. 100 mL of THF and 200 mL of ethyl acetate were added and dissolved the residue (intermediate E). This solution of intermediate E was subjected to the subsequent step of the reaction.
(Synthesis of Intermediate G)
250 mL of dimethylacetamide and 250 mL of acetonitrile were added to 51.8 g (0.25 mol) of intermediate F obtained in accordance with the procedure described in JP-A-2001-33921 and agitated at room temperature. 41.8 g (0.28 mol) of dimethylaniline was added to this solution. Then, a THF/ethyl acetate solution of intermediate E obtained by the above procedure was dropped to this solution. The reaction solution was agitated at 30xc2x0 C. for 3 hr to complete the reaction. After the completion of the reaction, 10 mL of concentrated hydrochloric acid was added, then, extraction was effected by adding 700 mL of ethyl acetate and 2000 mL of water. This ethyl acetate solution was washed thrice with brine. The ethyl acetate solution was concentrated under reduce pressure to obtain oily intermediate G quantitatively. The oily substance (intermediate G) was dissolved to 500 mL of isopropanol, and subjected to the subsequent step of the reaction.
(Synthesis of Intermediate H)
40 mL of water and 700 mL of isopropanol were added to 160 g of reduced iron and 5 g of ammonium chloride, and heated to reflex while agitating. To the suspension, 1 mL of acetic acid was added. Then, the solution of intermediate G obtained by the above procedure was dropped thereinto. After the completion of the addition, 700 mL of ethyl acetate was added and heated while agitating. Insoluble materials were filtered of while the reaction solution was hot. The filtrate was washed with water, and the solvent was distilled-off under reduced pressure. 500 mL of ethyl acetate was added to the residue, and precipitated crystal. The crystal was harvested by filtration, and dried to obtain 86.0 g (yield: 57.8%) of intermediate H.
(Synthesis of Exemplified Coupler MA-7)
180 mL of dimethylacetamide was added to 59.5 g (0.1 mol) of intermediate H obtained by the above procedure, and agitated at room temperature. 100 mL of ethyl acetate solution to which 34.1 g (0.11 mol) of intermediate C obtained by the above procedure was dissolved, was dropped thereinto. After the completion of the dropping, the solution was agitated at room temperature for 2 hr to complete the reaction. After the completion of the reaction, 700 mL of water and 500 mL of ethyl acetate were added for extraction. The ethyl acetate solution was washed with water and dried. Ethyl acetated was concentrated under reduced pressure. 700 mL of acetonitril and 120 mL of ethyl acetate were added to the residue to precipitate crystal. The crystal was harvested by filtration and dried to obtain 67.0 g (yield: 77.2%) of the exemplified coupler MA-7. The melting point of thereof was 78xc2x0 C. to 84xc2x0 C.
Exemplified Coupler M-16 was synthesized in accordance with the following reaction scheme B. 
(Synthesis of Intermediate I)
900 mL of dimethylacetamide was added to 304.5 g (1.0 mol) of 3-pentadecylphenol, and agitated at room temperature. 210 mL of a 28% methanol solution of sodium methoxide was added to the 3-pentadecylphenol solution. 201.6 g (1.0 mol) of 2-chloro-5-nitrobenzoic acid was added to the resultant solution. Thereafter, 276 g of potassium carbonate was added to the solution, and heated at 130 to 138xc2x0 C. and agitated. The heating and agitation was continued for 5 hr, and the resultant reaction mixture was cooled to room temperature. The thus formed crystal was filtered off, and the obtained filtrate was poured into 5000 mL of water, thereby obtaining an aqueous solution. 100 mL of concentrated hydrochloric acid was added to the aqueous solution under agitation, so that the aqueous solution was acidified, thereby effecting crystallization. The crystal was harvested by filtration, and washed with water. The obtained crystal was recrystallized from 1200 mL of acetonitrile, and dried. Thus, 400 g (yield: 85.2%) of intermediate I was obtained.
(Synthesis of Intermediate J)
450 mL of toluene was added to 140.9 g (0.3 mol) of intermediate I obtained in the above procedure, and heated at 90xc2x0 C. and agitated. 33 mL of thionyl chloride was dropped into the intermediate I solution. After the completion of dropping, the mixture was heated and agitated for 2 hr to thereby complete the reaction. The resultant reaction mixture was cooled to room temperature, thereby obtaining a toluene solution of intermediate J. This solution was subjected to the subsequent step of reaction.
(Synthesis of Intermediate F)
330 mL of isopropyl alcohol was added to 111.3 g (0.33 mol) of intermediate X obtained in accordance with the procedure described in JP-A-2001-33921 and 30.2 g of sodium hydrogen carbonate, and heated and refluxed under agitation, thereby obtaining a solution. 18 g of hydrazine monohydrate was dropped into the solution. After the completion of dropping, the mixture was heated and refluxed under agitation for 2 hr to thereby complete the reaction. The resultant reaction mixture was cooled to room temperature, and 300 mL of water and 42.5 mL of concentrated hydrochloric acid were added thereto. The thus obtained solution was agitated for 1 hr, and crystals of phthalohydrazide were filtered off in vacuum. Thus, an aqueous solution of intermediate F hydrochloride was obtained, and subjected to the subsequent step of reaction.
(Synthesis of Intermediate K)
800 mL of ethyl acetate was added to the aqueous solution of intermediate F (0.33 mol) obtained in the above procedure, and agitated at room temperature. 250 g of sodium hydrogen carbonate was divided into portions and sequentially added to the intermediate F solution. Subsequently, the toluene solution of intermediate J (0.3 mol) obtained in the above procedure was dropped into the intermediate F solution. After the completion of dropping, the mixture was agitated at room temperature for 1 hr to thereby complete the reaction. After the completion of reaction, a water layer was removed from the reaction mixture, and the remaining ethyl acetate layer was washed with water. The resultant ethyl acetate solution was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off in vacuum. Thus, waxy intermediate K was obtained. 500 mL of isopropanol was added to the obtained waxy intermediate K, and heated to thereby effect dissolution. The isopropanol solution of intermediate K was subjected to the subsequent step of reaction.
(Synthesis of Intermediate L)
1 mL of acetic acid, 80 mL of water and 300 mL of isopropanol were added to 200 g of reduced iron and 20 g of ammonium chloride, and heated and agitated to thereby obtain a solution. The isopropanol solution of intermediate K obtained in the above procedure was dropped into the iron solution. After the completion of dropping, the mixture was heated and agitated for 2 hr to thereby complete the reaction. After the completion of reaction, 750 mL of ethyl acetate was added to the reaction mixture, and agitated. The resultant mixture was subjected to hot filtration in vacuum, thereby removing insoluble substance. Thereafter, water was added to the filtrate to thereby separate an ethyl acetate layer. Water layer was removed, and the ethyl acetate layer was further washed with water. The ethyl acetate solution was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off in vacuum. Thus, amorphous intermediate L was obtained in approximately a quantitative amount. Dimethylacetamide was added to the obtained amorphous intermediate L to thereby effect dissolution and to make the total amount to 600 mL. This dimethylacetamide solution was subjected to the subsequent step of reaction.
(Synthesis of Coupler Example M-16)
600 mL of the dimethylacetamide solution of intermediate L (0.3 mol) obtained in the above procedure was cooled and agitated at 10xc2x0 C. 84.0 g (0.3 mol) of 2,4,5-trichlorobenzenesulfonyl chloride was divided into several portions and added to the intermediate L solution. Then, 29.0 mL (0.36 mol) of pyridine was dropped thereto. After the completion of dropping, the mixture was agitated at room temperature for 5 hr to thereby complete the reaction. After the completion of reaction, 800 mL of ethyl acetate and 1200 mL of water were added to the reaction mixture to thereby effect an extraction. Water ethyl acetate solution was washed with brine and dried over anhydrous magnesium sulfate. The ethyl acetate solution was concentrated under reduced pressure. 600 mL of acetonitrile and 200 mL of ethyl acetate were added to thereby effect crystallization. The crystal was recrystallized from a mixed solvent of acetonitrile and ethyl acetate, to obtain 153.8 g (yield: 58.8%) of Exemplified Coupler M-16. The melting point was 83 to 94xc2x0 C.
Exemplified Coupler M-50 was synthesized in accordance with the following reaction scheme C. 
(Synthesis of Compound M)
196 g of concentrated sulfuric acid was heated at 100xc2x0 C. and agitated, and 134.2 g (1.0 mol) of isobutylbenzene was dropped thereinto. After the completion of dropping, the mixture was agitated at 110 to 115xc2x0 C. for 2 hr. The resultant reaction mixture was cooled to 40xc2x0 C., and 350 g of chlorosulfonic acid was dropped thereinto. After the completion of dropping, a reaction was effected at room temperature for 2 hr. After the completion of reaction, the reaction mixture was poured into 3 liter (hereinafter liter is also referred to as xe2x80x9cLxe2x80x9d) of ice water under agitation. 800 mL of n-hexane and 200 mL of ethyl acetate were added to the thus obtained aqueous solution to thereby effect an extraction. The thus obtained n-hexane/ethyl acetate mixture solution was washed with water, and dried over anhydrous sodium sulfate. The resultant n-hexane/ethyl acetate solution was concentrated in vacuum. Thus, 163 g (yield: 70%) of oily intermediate M was obtained.
(Synthesis of Intermediate N)
300 mL of acetonitrile was added to 75.6 g (0.5 mol) of methyl anthranilate, and agitated at room temperature. 116.4 g (0.5 mol) of intermediate M obtained in the above procedure was dropped into the acetonitrile solution. Subsequently, 44.5 mL (0.55 mol) of pyridine was dropped thereinto. After the completion of dropping, a reaction was effected at room temperature for 5 hr. After the completion of reaction, the reaction mixture was poured into 1500 mL of water under agitation, thereby attaining crystallization. The crystal was harvested by filtration, washed with water, dispersed in 300 mL of methanol to thereby effect washing, harvested by filtration, and dried. Thus, 160 g (yield: 92.1%) of intermediate N was obtained.
(Synthesis of Intermediate O)
450 mL of methanol was added to 139 g (0.4 mol) of intermediate N obtained in the above procedure, and agitated at room temperature. An aqueous solution obtained by dissolving 67.2 g of potassium hydroxide in 130 mL of water was added to the compound N solution. After the completion of addition, the reaction mixture was heated and refluxed to thereby effect further reaction for 1 hr. After the completion of reaction, the reaction mixture was cooled to room temperature, and poured into an aqueous solution of hydrochloric acid obtained by adding 200 mL of water to 110 mL of concentrated hydrochloric acid, thereby effecting crystallization. The thus obtained crystal was harvested by filtration, washed with water and dried. Thus, 124 g (yield: 93%) of intermediate O was obtained.
(Synthesis of Intermediate P)
300 mL of toluene was added to 100 g (0.3 mol) of intermediate O obtained in the above procedure, and heated at 100xc2x0 C. and agitated. 32.9 mL (0.45 mol) of thionyl chloride was dropped into the intermediate O solution. After the completion of dropping, the mixture was agitated at 100xc2x0 C. for 2 hr to continue reaction. After the completion of reaction, the reaction mixture was cooled to room temperature, thereby obtaining a toluene solution of intermediate P. This solution was subjected to the subsequent step of reaction.
(Synthesis of Exemplified Coupler M-50)
The dimethylacetamide solution of intermediate L (0.3 mol) obtained in the above procedure was agitated at room temperature. The toluene solution of intermediate P (0.3 mol) obtained in the above procedure was dropped into the compound J solution. After the completion of dropping, the mixture was agitated at room temperature for 3 hr to thereby complete the reaction. After the completion of reaction, 800 mL of ethyl acetate and 800 mL of water were added to the reaction mixture to thereby effect an extraction. Water layer was removed, and the ethyl acetate/toluene mixture layer was washed with water and dried over anhydrous magnesium sulfate. Ethyl acetate and toluene were distilled off in vacuum. 1000 mL of acetonitrile was added to the distillation residue to thereby effect crystallization. The crystal was harvested by filtration and purified by recrystallization from a solvent composed of a 6/1 mixture of acetonitrile/ethyl acetate. Thus, 207.9 g (yield: 72.0%) of Exemplified Coupler M-50 was obtained.
1HNMR (CDCl3) 10.42 (s, 1H), 9.18 (s, 1H), 8.72 (d, 1H), 8.25 (s, 1H), 8.04 (d, 1H), 7.99 (d, 1H), 7.73-7.50 (m, 4H), 7.40 (t, 1H), 7.30-7.20 (m, 1H), 7.16-6.97 (m, 4H), 6.95-6.78 (m, 3H), 5.75-5.58 (m, 1H), 5.51 (s, 1H), 2.59 (t, 2H), 2.38 (d, 2H), 1.85-1.68 (m, 1H), 1.65-1.48 (m, 5H), 1.41-1.15 (m, 33H), 0.88 (t, 3H), 0.80 (d, 6H).
The photosensitive material of the present invention is characterized in that at least one 1H-pyrazolo[3,2-c]-1,2,4-triazole type coupler having a substituent represented by the general formula (I) is contained, preferably in at least one silver halide emulsion layer. The photosensitive material of the present invention is also characterized in that at least one coupler represented by the general formula (III) or general formula (IV) is contained, preferably in at least one silver halide emulsion layer.
The total content of the couplers of the present invention in the photosensitive material is preferably in the range of 0.01 to 10 g, more preferably 0.1 to 2 g, per m2 of the photosensitive material. The suitable total content per mol of silver halides contained in emulsion layers of identical lightsensitivity is in the range of 1xc3x9710xe2x88x923 to 1 mol, preferably 3xc3x9710xe2x88x923 to 3xc3x9710xe2x88x921 mol.
It is preferred that the compound SR-1 and couplers of the present invention be used in the same layer. Although compounds as obtained by changing a substituent of the compound SR-1, for example, those as obtained by changing t-octyl of the compound SR-1 to n-octyl, n-hexadecyl, t-butyl or the like and as obtained by changing isopropyl of the compound SR-1 to methyl, ethyl or the like can be used in the same manner, the compound SR-1 itself is most preferred.
The amount of compound SR-1 used can be in the range of 0.1 to 200 mol % per mol of couplers of the present invention. The amount is preferably in the range of 5 to 100 mol %, more preferably 5 to 20 mol %.
The process for synthesizing the compound SR-1 is described in Jpn. Pat. Appln. KOKOKU Publication No. (hereinafter referred to as JP-B-) 45-14034.
In the silver halide color photosensitive material of the present invention, various additives can be used in conformity with the object thereof.
These additives are described in detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979) and Item 308119 (December 1989), all the contents of which are incorporated herein by reference. A summary of the locations where they are described will be listed in the following table.
With respect to the layer arrangement and related techniques, silver halide emulsions, dye-forming couplers, DIR couplers and other functional couplers, various additives and development processing which can be used in the photosensitive material of the present invention, reference can be made to EP 0565096A1 (published on Oct. 13, 1993) and patents cited therein, all the contents of which are incorporated herein by reference. Individual particulars and the locations where they are described will be listed below.
1. Layer arrangement: page 61 lines 23 to 35, page 61 line 41 to page 62 line 14,
2. Interlayers: page 61 lines 36 to 40,
3. Interlayer effect-imparting layers: page 62 lines 15 to 18,
4. Silver halide halogen compositions: page 62 lines 21 to 25,
5. Silver halide grain crystal habits: page 62 lines 26 to 30,
6. Silver halide grain sizes: page 62 lines 31 to 34,
7. Emulsion production methods: page 62 lines 35 to 40,
8. Silver halide grain size distributions: page 62, lines 41 to 42,
9. Tabular grains: page 62 lines 43 to 46,
10. Internal structures of grains: page 62 lines 47 to 53,
11. Emulsions of latent image-forming types: page 62 line 54 to page 63 to line 5,
12. Physical ripening and chemical sensitization of emulsion: page 63 lines 6 to 9,
13. Emulsion mixing: page 63 lines 10 to 13,
14. Fogged emulsions: page 63 lines 14 to 31,
15. Nonlightsensitive emulsions: page 63 lines 32 to 43,
16. Silver coating amounts: page 63 lines 49 to 50,
17. Formaldehyde scavengers: page 64 lines 54 to 57,
18. Mercapto-type antifoggants: page 65 lines 1 to 2,
19. Fogging agent, etc.-releasing agents: page 65 lines 3 to 7,
20. Dyes: page 65, lines 7 to 10,
21. Color coupler summary: page 65 lines 11 to 13,
22. Yellow, magenta and cyan couplers: page 65 lines 14 to 25,
23. Polymer couplers: page 65 lines 26 to 28,
24. Diffusive dye forming couplers: page 65 lines 29 to 31,
25. Colored couplers: page 65 lines 32 to 38,
26. Functional coupler summary: page 65 lines 39 to 44,
27. Bleaching accelerator-releasing couplers: page 65 lines 45 to 48,
28. Development accelerator release couplers: page 65 lines 49 to 53,
29. Other DIR couplers: page 65, line 54 to page 66 to line 4,
30. Method of dispersing couplers: page 66 lines 5 to 28,
31. Antiseptic and mildewproofing agents: page 66 lines 29 to 33,
32. Types of sensitive materials: page 66 lines 34 to 36,
33. Thickness and swelling speed of lightsensitive layer: page 66 line 40 to page 67 line 1,
34. Back layers: page 67 lines 3 to 8,
35. Development processing summary: page 67 lines 9 to 11,
36. Developers and developing agents: page 67 lines 12 to 30,
37. Developer additives: page 67 lines 31 to 44,
38. Reversal processing: page 67 lines 45 to 56,
39. Processing solution open ratio: page 67 line 57 to page 68 line 12,
40. Development time: page 68 lines 13 to 15,
41. Bleach-fix, bleaching and fixing: page 68 line 16 to page 69 line 31,
42. Automatic processor: page 69 lines 32 to 40,
43. Washing, rinse and stabilization: page 69 line 41 to page 70 line 18,
44. Processing solution replenishment and recycling: page 70 lines 19 to 23,
45. Developing agent built-in photosensitive material: page 70 lines 24 to 33,
46. Development processing temperature: page 70 lines 34 to 38, and
47. Application to film with lens: page 70 lines 39 to 41